Unsaturated esters and polymers thereof



Fatented Apr. 30, 1946 UNITED STATES PATENT OFFICE UNSATURATED ESTERS AND POLYMERS THEREOF No Drawing. Application November 25, 1942, Serial No. 466,950

8 Claims. (Cl. 26078) in which R is the radical derived by esteriflcation 1 from the simple polyhydroxy compound having a:

hydroxyl groups, R1 is a hydrogen, hydrocarbon or substituted hydrocarbon radical attached to the alpha carbon atom of the hydroxy acid and R2 is the radical derived by the esteriflcation of an unsaturated alcohol.

By "ester linkage we mean a linking oxygen atom derived by reaction of an hydroxyl group and an acid group. Thus, a carbonate Rr-C0O--R contains two ester linkages.

By simple polyhydroxy compound" we mean any organic compound having two or more hydroxyl groups which are not separated by an ester linkage. Thus, bis (hydroxyethyl) carbonate is not a simple polyhydroxy compound. Suitable simple poly-hydroxy compounds are the glycols such as ethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,3-dihydroxybutane, the dihydroxy petanes, ricinoleyl alcohol, etc., the polyglycols such as di-, tri-, and tetraethylene glycol, di-, tri-, and tetrapropylene glycol, di-, tri-, and tetrabutylene glycols, etc., the homocyclic polyhydroxy compounds such as resorcinol, pyrogallol, catechol, etc., or the higher polyhydroxy aliphatic compounds such as glycerol, erythritol, pentaerythritol, dextrose, sucrose, etc.

By simple alpha hydroxy acid" we mean an aliphatic monocarboxylic acid which has an bydroxy group attached to the carbon atom immediately adjacent to the carboxylic group. Suitable alpha. hydroxy acids are glycolic, lactic, acetonic, valerolactinic, leucinic, and a-hydroxy butyric acids, etc.

The new compounds are preferably the esters or unsaturated alcohols having up to five carbon atoms and an unsaturated linkage in an aliphatic chain such as vinyl, allyl,-methallyl, 2-chloroallyl, crotyl, tiglyl, chlorocrotyl, 2-bromoallyl, ethylallyl, propargyl, methylpropargyl, and angelyl alcohols, methyl vinyl carbinol, ethyl vinyl carbinol, etc. Esters of alcohols having six to ten carbon atoms are also useful such as geranyl, cinnamyl, p-propylallyl and phenylpropargyl a1- cohols, ethyl divinyl carbinol, etc.

The new esters may be prepared by treating the simple polyhydroxy compound with an excess of phosgene to form polychloroformates such as ethylene glycol bis chloroformate, diethylene glycol bis chloroformate, pentaerythritol tetrakls chloroformate, resorcinol bis chloroformate, etc., which are subsequently reacted with unsaturated alcohol esters of the alpha hydroxy acids such as allyl e-hydroxy-butyrate,methallyl glycclate, vinyl valerolactinate, etc. The chloroformate preparation is preferably conducted at temperatures between 0 C. and C. by bubbling the phosgene'slowly through the simple polyhydroxy compound or a solution of it in benzene, ether, carbon tetrachloride, petroleum ether, or other suitable solvent. Use of ice or other cooling medium is usually required to dissipate the heat of reaction. The esterification may be conducted at low temperatures, preferably below C., by adding the chloroformate to a mixture of the unsaturated ester and an alkaline reagent such as pyridine or other tertiary cyclic amine, or a carbonate, oxide, or hydroxide of an alkali or alkaline earth metal. When an insoluble alkali such as calcium carbonate is used it is frequently necessary to use elevated temperatures, for example, to C., in order to induce a satisfactory rate of reaction. When strongly alkaline reagents such as sodium hydroxide are used, it may be necessary to reverse the preferred method of combining the reagents by adding the alkali to the chloroformate to prevent a large excess of strong alkali from existing in the solution with the ester being synthesized.

The same new esters may be alternatively prepared by treating the unsaturated alcohol ester of the simple hydroxy acid, such as allyl lactate,

vinyl leucinate, tiglyl glycolate, etc., with phosene to form the corresponding chloroformate.

The reaction is preferably conducted at subnormal temperatures maintained by artificial cooling and may be conducted in the presence of a The new unsaturated carbonates are generally non-resinous compounds having distinct boilin and melting points and are often capable of isolation in substantially pure state. Frequently, the' impurities are side reaction products which are colorless and transparent esters having characteristics similar to the esters herein contemplated. In such cases, removal of said impurities may be unnecessary unless they produce a detrimental effect in the use towhich the ester is put. The new compounds are usually, liquids at normal temperatures but some, however, are solids. The new unsaturated compounds are usually miscible with solvents such as benzene, toluen'e, chloroform, dlethyl ether, carbon tetrachloride and petroleum ether. The monomeric esters are valuable as plasticizers for various resin materials such as styrene, cellulose, vinyl, urea, protein, phenolic, or acrylic resins. Other uses such as solvents, insecticides, and liquid coating compositions are noteworthy.

These esters may be polymerized in the presence of heat, light, or catalysts such as oxygen, ozone, or organic peroxides such as lauroyl, benzoyl, or acetone peroxides to yield solid or liquid compositions of widely diflering physical properties. The polymerized products vary in properties, depending upon the structure 01' the ester and upon the degree of polymerization.

These polyunsaturated esters are capable of polymerization to a fusible intermediate stage and finally to a substantially infusible and insoluble polymer. The ultimate polymer of these new compounds are generally highly resistant to acids, alkalies, water, and organic solvents. The polymers thus obtained are usually colorless and transparent, although in somelnstances they may be slightly yellow when polymerized completely. Many of these polymers are tough and quite resistant to shattering.

Upon the initial polymerization of the polyunsaturated esters in the liquid monomeric state or in a solution of the monomer in suitable solvents, an increase in the viscosity of the liquids is noticeable due to the formation of a simple polymer which is soluble in the monomer and in solvents such as acetone, benzene, xylene, dicxane, toluene, or carbon tetrachloride. Upon further polymerization, the liquid set up to form a soft gel containing a substantial portion of a polymer which is insoluble in the monomer and organic. solvents and containing as well, a substantial portion of a soluble material which may be monomer and/or fusible soluble polymer. These gels are soft and bend readily. However, they are fragile and crumble or tear under low stresses. They may be further polymerized in the presence of catalysts to the final infusible insoluble state in which substantially all of the polymer is infusible and insoluble in organic solvents, acids. and alkalies.

The monomers of the polyunsaturated esters may be cast polymerized directly to the substantially insoluble, infuslble state. This procedure is subject to certain inherent difiiculties due to the strains which are established during polymerization of the gel and which frequently result in fractures as the final hard form is attained. It has been discovered that these difiiculties may be avoided by releasing the strains established in the gel before the fracturing can occur. This may be done by permitting the strains to be relieved before the polymerization is complete, either periodically or by conducting the polymerization under conditions which permit gradual release of aaoaasr these strains. For example, the polymerization may be conducted in a simple mold until a soft firm gel has formed. At this point the P lymer may be freed from the mold to which it adheres strongly. When released the polymer contracts substantially, thereby relieving the polymerization strains. The gel may thereafter be shaped. if desired, and polymerized to the final ini'usible state. Smooth, optically perfect sheets may be made by this method. Preferably, the initial olymerization is conducted at a temperature suificiently low to prevent the complete decomposition of the peroxide catalyst. This temperature is dependent upon the catalyst used. For benzoyl peroxide, temperatures of 65 to C. are suitable, while for acetone peroxide temperatures of C. may be used. In accordance with one modification, the gel, after it is freed from the mold, may be coated on both sides with monomer or the syrupy polymer. The coated article is then polymerized between smooth heated plates to the final insoluble state.

Other intermediate polymers of a more advanced state of polymerization may be prepared by continuing the heating of a soft gel which contains residual peroxide. These may be hard at normal room temperatures and may contain appreciable quantities of both the aceton soluble and acetone insoluble polymers. These advanced polymers become more flexible at higher temperatures and may be shaped after heating. Preferably, the shaping does not exceed the elastic limit of the material. The flexible sheet is held in its flexed position in a mold or other shap ing device until cooled to the normal room temperature. A permanently shaped resin is thereby formed which may contain simpleor complex curvatures.

Cast polymers may also be prepared by a single step polymerization directly to the insoluble state. The monomer may be mixed with one to five percent of benzoyl or other organic peroxide and heated at 5060 C. until it becomes partly polymerized and thickened to an increased viscosity of 100 to 1000 percent of the monomer viscosity. The thickened monomer may then be polymerized between glass, metal, or similar plates which are separated by compressible gaskets or retainers of Koroseal (plasticized polyvinyl chloride), butadlene. polymers, polyvinyl alcohol, Thiokol (polyethylene sulfide), rubber, or similar materials arranged about the edge of such plates. The thickened monomer may be poured on one glass plate within the confines of the flexible retainer, laid about two inches from the edge of the plate. The second glass plate may then be carefully laid on top, taking care to avoid the trapping of air bubbles under the top plate. When the top plate is in position, both plates may be held together by means of suitable clamps which are capable of applying pressure upon the plates directly over the flexible retainer. The entire assembly is then placed in an oven and heated at '70 to 100 C. where the polymerization is continued. During the polymerization the resin shrinks and tends to draw away from the glass surfaces. To prevent fractures, sufilcient pressure is maintained upon the plates to depress the flexible container and minimize or prevent lateral or longitudinal shrinkage while the resin is polymerized within the mold. This pressure may be maintained by periodically tightening the clamps or by use of spring clamps which maintains a uniform pressure throughout the polymerization process.

By an alternative process for cast polymerizing sheets, the molds may be assembled before the thickened monomer is poured. Thus, the flexible compressible retainer may be inserted between the plates and held in place by suitable clamps located around the edge of the plates. This retainer or gasket is placed adjacent to the edge of the plates and a suitable opening may be provided between the ends of the flexible retainer, preferably at one corner of the mold. The assembled mold is then placed in a vertical position with the open corner uppermost. The thickened monomer containing up to five percent residual peroxide is then poured in slowly until the entire mold is filled. After standing until all of the entrapped air has separated the mold is sealed and heated uniformly between '70 and 100 C. to continue the polymerization. Pressure is maintained upon the plates to prevent lateral or longitudinal shrinkage of the resin during polymerization by suitable means such as by tightening the clamps periodically or by maintaining a uniform pressure upon the plates throughout by means of spring clamps. When the resin has been completely polymerized it is separated from the glass plates and a hard, transparent, colorless, and durable resin sheet is obtained.

Other methods have been developed for polymerization of the compounds herein contemplated while avoiding formation of cracks and fractures. By one of these methods the polymerization may be suspended while the monomerpolymer mixture is in the liquid state and before the polymer is converted to a gel by cooling, by removal from exposure to ultraviolet light, by adding inhibiting materials such as pyrogallol, hydroquinone, aniline, phenylene diamine, or sulphur, or by destruction of the polymerization catalyst. The fusible polymer may be separated from all or part of the monomer by any of several methods. It may be precipitated by the addition of nonsolvents for the fusible polymer such as water, ethyl alcohol, methyl alcohol, or glycol. The fusible polymer is thus obtained in stable solid form and as such may be used, as a molding powder or may be redissolved in suitable solvent for use in liquid form. It is soluble in organic solvents such as benzene, chloroform, ethyl acetate, acetone, toluene, etc. Preferably, the polymers of the new esters are produced by heating the monomer or a solution thereof in the presence of substantial quantities, for example, up to percent of benzoyl peroxide until the viscosity 'of the solution has increased about 100 to 500 percent. This may require several hours while heating at 65 to 85 C. in the presence of benzoyl peroxide. The resulting viscous solution is poured into an equal volume of water, methyl or ethyl alcohols, glycol, or other nonsolvent for the fusible polymer. A polymer usually in the form of a powder or a gummy precipitate is thus formed which may be decanted or filtered and then dried. This permits substantially complete separation of a soluble fusible polymer from unpolymeri'zed monomer.

Often, however, a complete separation of monomer and polymer is not desirable since hazy products may be secured upon further polymerization. Accordingly, it is often desirable to produce compositions comprising the fusible polymer and the monomer. This may be effected by partial distillation or extraction of monomer from the polymer or by reblending a portion of the fusible polymer with the same or a different. polymerizable monomer. -In general, such a composition may contain soluble fusible polymer in amount up to 50 or 60 percent. Preferably, the production of these materials is conducted by treatment of a solution of the monomer in a solvent for monomer and intermediate polymer such as benzene, xylene, toluene, carbon tetrachloride, acetone, chloroform, ethyl acetate, etc.

Other polymerizable methods may involve the interruption of the polymerization while the polymer is a gel. For example, a soft solid gel containing a substantial portion of fusible polymer may be digested with a quantity of solvent for the fusible polymer to extract the fusible gel from the infusible. The solution may then be treated as above described to separate the fusible polymer from the solvent. These polymers may be used as molding or coating compositions.

Other fusible polymers may be prepared by carrying the initial polymerization to the pointwhere the polymer is in the form of a gel which generally contains at least 20 percent and preferably about 45 to 90 percent by weight of substantially insoluble polymer, but at which point the gel is still fusible. This solid resin composition may be disintegrated to a pulverulent form and used as a molding powder. Alternatively, then, a desirable polymer may be prepared by emulsifying the monomer of a syrupy polymer in an aqueous medium with or without a suitable emulsification agent such as polyvinyl alcohols, polyallyl alcohols, etc., and then polymerizing to the point where the gel precipitates. This polymer may be separated and used as molding powder.

The solid forms of the fusible polymers may be used as molding compositions to form desirable molded products which may b polymerized to a thermohardened state. Preferably, the molding is conducted in a, manner such that the polymer fuses or blends together to form a substantially homogeneous product before the composition is polymerized to a substantially infusible state. This may be effected by conducting polymerization at an elevated temperature and/or pressure in the presence of benzoyl peroxide, generally in a heated mold. The polymers may be mixed with fillers such as alpha cellulose, wood pulp, and other fibrous substances, mineral fillers, or pigments such as zinc oxide, calcium carbonate, lead chromate, magnesium carbonate, calcium silicate,

etc., and plasticizers such as the saturated alcohol esters of phthalic acid, camphor, the saturated alcoh'ol esters of maleic, fumaric, succinic, and adipic acids or dior triethylene glycol bis (butyl carbonate). The polymeric molding powder may be copolymerized with phenolic, cellulose acetate, urea, vinylic, protein, or acrylic resins. It is thus possible to produce transparent or opaque forms of a wide variety of colors and hardnesses, depending upon the proper selection of the modifying agents.

The soluble fusible polymers may be dissolved in suitable solvents and used as coating and impregnating compositions. For example, the solution or dispersion of fusible polymer in monomer or other organic solvent such as benzene, toluene, chloroform, acetone, dioxane, carbon tetrachloride. phenyl Cellosolve, dichloroethyl eth'er, dibutyl phthalate, or mixtures thereof, is useful as a liquid coating composition. Objects of paper. metal, cloth, wood, leather, or synthetic resins may be coated with the solution of polymer in solvent'and subsequently polymerized to yield attractively finished coatings. Similarly, porous objects of felt, cloth, leather, paper, etc., either in single layers or laminated, may beimpregnated pressure to a glossy solid polymer of high tensile.

strength. The use of too much filler may cause a non-glossy finish and the use of too much monomer may make the powder moist and diflicult to handle. Sometimes it may be desirable to precure the molding powder by subjecting it to a moderate temperature, 50 to 70 C., for a limited period of time, for example, one to three'hours. This precuring operation is a partial polymerization and permits a dry molding powder where the same proportions of monomer might result in a moist molding composition.

Further details of the synthesis of these new esters and of their applications will be apparent from the following examples.

Example 1 Equal molar parts of methallyl alcohol (300.6 grams) and glycolic acid (281 grams) were heated for 18 hours on an oil bath at the reflux temperature. The water was separated from the condensate before returning the latter to the system. The methallyl glycolate was washed with water and distilled in vacuum. The purified methallyl glycolate was cooled to C. on a salt-ice mixture and treated with phosgene at a rate which permitted the reaction temperature to remain below +8 C. When the reaction was complete the mixture was heated to remove any excess phosgene.

Approximately 200 grams of the chloroformate of meth'allyl glycolate were reacted with 7 grams of propylene glycol. The reaction was conducted in the presence of 100 grams of pyridine and 500 cc. benzene and at a temperature of 0 to 12 C., maintained by stirring the mixture vigorously while the flask was immersed in a freezing mixture. The chloroiormate was added slowly to the propylene glycol at a rate which permitted the dissipation of the heat of the reaction. The benzene solution was washed with dilute hydrochloric acid and water. The mixture was decolorized by heating for one hour with one gram of activated charcoal while driving 01! the benzene. The pressure was reduced to 2 to 3 mm. and heated to remove benzene and the excess reactants. A colorless liquid remained which was proved to have the structure:

A fifty gram sample of the ester containing 3 percent benzoyl peroxide was dissolved in 300 cc. of benzene and heated until the viscosity had increased about 500 percent. The viscous solution was then poured into 500 cc. of methyl alcohol. After standing over night, a precipitated gel polymer was separated by decanting. After washing with water and drying the polymer was a white granular material.

A ten gram sample was mixed with 3 percent benzoyl peroxide and pressed at 1500 pounds per square inch and at 135 C. a colorless. transparent solid resin was produced.

Example II A large excess (210 grams) 0! crotyl alcohol, 105 grams of alpha hydroxy butyric acid and 2 grams p-toluenesulphonic acid were esterifled by heating for 30 hours at reflux temperature. The water evolved was slowly removed by distillation during the reaction. The crotyl a-hydroxy butyrate was freed of impurities by distillation.

Eighty grams of the bischloroiormate of trimethylene glycol was mixed with 500 cc. of benzene and 100 grams of the crotyl a-hydroxy butyrate. Seventy-five cubic centimeters of a prepared 50 percent solution of NaOH was slowly added with continuous stirring and the reaction flask submerged in an ice bath. The reaction temperature did not rise above 11 C. The benzene solution was washed with dilute hydrochloric acid until neutral to phenolphthalein and with water. After drying over calciumchloride the benzene was removed by topping at 35-40 mm. pressure. The ester was believed to have the following structure:

L 2K5 O H: e 02H:

Allyl lactate was prepared by heating a mixture of 739' cc. of percent lactic acid, 2041 cc. of allyl alcohol, 9 grams of p-tcluenesulphonic acid, and 1000 cc. of carbon tetrachloride on an oil bath for 24.5 hours at reflux temperature. The condensate was divided into the two liquid phase fractions and the nonaqueous phase was returned to the reaction flask. The allyl lactate was distilled at 96 C. (30 mm.). 120 grams of diethylene glycol dichloroformate was cooled to +5 0. and added slowly (3 to 4 grams per minute to a mixture of 100 grams of allyl lactate and 85 grams of pyridine. The reaction flask was equipped with a mechanical stirring device and was surrounded by a. bath of a salt-ice freezing mixture. During the reaction the temperature within the flask did not rise above 16 C. When the reaction was completed the ester was washed with dilute hydrochloric acid and with water until neutral. It was a clear liquid believed to have the structure:

A ten gram sample was mixed with 0.3 gram of lauroyl peroxide and heated at 75 C. for two hours. A hard, light-colored polymer was produced.

Example IV Using the procedure described in Example III but substituting ethylene glycol dichloroiormate for the diethylene glycol dichloroformate, the ethylene glycol ester homologous to the diethylene glycol ester of Example III was prepared.

Although the present invention has been described with respect to certain specific examples,

it is not intended that the details thereof shall be limitations upon the scope of the invention exlyloxy) (methyl) carblnylcarbonic acid] ester having the structure:

4. A polymer of the compound defined in claim 1.

5. A polymer of the compound defined in claim 2.

6. A polymer of the compound defined in claim 3.

7. A compound havin: the structural formula:

wherein R is a divalent alkylene radical, R1 is a radical selected from the group consisting of hydrogen and saturated alkyi radicals and R: is a radical corresponding to the radical R: in the alcohol RzOH, said alcohol having from 2 to 10 carbon atoms and having an unsaturated carbon to carbon linkage in an aliphatic chain. said unsaturated linkage being adjacent the beta carbon atom of the alcohol.

8. A polymer of a compound as defined in claim 7.

IRVING E. MUBKAT. FRANKIJN STRAIN. 

